Fuel oil composition



2,996,364 FUEL OIL COMPOSITION Raymond Gay and Emanuel Siganos, Notre-Dame-de- Gravenchon, France, assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed June 17, 1958, Ser. No. 742,494 Claims priority, application France June 20, 1957 7 Claims. (Cl. 4462) The present invention relates to an improved fuel oil.

The words fuel oil are herein defined as a normally liquid hydrocarbon for example a petroleum distillate boiling above about 400 F. and including light fuel oils, gas oils, used as fuels for diesel engines, and heavy oils used in furnaces.

To increase the power output of an internal combustion engine, for example, a diesel engine, it is common practice to inject an increased quantity of fuel into the combustion chamber. However, in the case of diesel engines, when the quantity of injected fuel exceeds certain critical limits, then a copious liberation of smoke occurs in the exhaust gases due to incomplete combustion of the fuel. Further, the increased power output which is obtained as a result of an increased injection of fuel is not directly proportional to the amount of fuel used. Consequently the specific consumption of the engine increases with increasing fuel injection.

It has previously been proposed to add oil-soluble lead salts to fuel oil particularly diesel oils to improve the anti-corrosive properties of the oils. Whilst these additives lessen the anti-corrosive properties of fuel oils having a high sulphur content, they have no effect on the combustion properties of the oil particularly the tendency to form smoke. a

It has now been discovered that it is possible to substantially improve the properties of the fuel oil, particularly the tendency to smoke by adding to the fuel oil a small proportion of a composition comprising an ashless detergent and the oil-soluble salt of a metal of group IV of the periodic table.

Lead salts are particularly preferred in the composition of the present invention. A mixture of the salts of the aforesaid metals may be used instead of the salt of one metal.

The oil-soluble metallic salts used in accordance with the present invention may be salts of fatty acids, for example, palmitic, stearic, erucic, oleic or ricinoleic acids, or salts of naphthenic abietic or sulphonic acids, or salts of any organic acid having more than 6 carbon atoms per molecule.

Any ashless detergent may be used in the present invention. It is preferred to use polymeric or copolymeric products containing an active detergent group, which may be obtained by incorporating in the polymeric or copolymeric chain sulphurised or phosphosulphurised groups, or nitrogenor oxygen-containing groups, and which may of may not contain alkoxy groups.

Suitable detergents may be built up of copolymerisable unsaturated monoand/or dibasic acids, or alkoxy derivatives thereof, including ester derivatives. Such products may be derived from C to C alcohols and maleic and/or fumaric acids, or mixtures of said esters including alkoxylated partial esters, and vinyl esters of C to C monobasic acids, e.g., vinyl acetate.

Other copolymeric compounds may be derived from alkyl-substituted acrylic acid and aliphatic alcohols, including amino alcohols.

Condensation products of an oil-soluble sulphonate and States Patent C an alkyl polyamine such as ethylene diamine and triethylamine may be also used as the ashless detergent in the composition of the present invention.

A mixture of the above detergents may be used instead of any particular detergent.

The total additive composition incorporated in the oils according to the present invention preferably comprises from 25 to 90% by weight of theoil-soluble salt of the said group IV metal and from 10 to 75% by weight of the said ashless detergent, and more particularly from 40 to by weight of the oil-soluble salt of the group IV metal and from 60 to 40% byweight of the ashless detergent, the percentage being based on the total additive compound.

The total quantity of detergent additive added to the fuel oil is preferably within the range of 0.001 to 0.5%

oil. 7

Fuel oil compositions prepared according to the present invention were tested on a General Motors diesel engine (G.M. 371) having the following characteristics:

No. of cylinder I 3 Bore (4%) mm 108 Stroke (5") mm 127 Cylinder capacity (212 cu. ins.) ..ccs 3490 Temperature of water C-.. 80 Temperature of oil C 107 EXAMPLE I A gas oil containing an additive in accordance with the present invention was used in a diesel engine of the type described above. The gas oil used had the following characteristics:

Density at 15 C 0.868 Engler Viscosity at 20 C 1.48 Sulphur, perc nt 1.08 Cetane index 43 The additive contained 50% by weight of an ashless detergent A and was added to the gas oil in quantities such that 1 kilogram of the oil contained 0.0005 gram atoms of metal.

The ashless detergent A was prepared as follows. Maleic anhydride was reacted with a C Oxo alcohol at 70 C., in the presence of a boron trifluoride/ether cornplex. One mole of the monoester obtained was then condensed with 3 moles of ethylene oxide. 8% by weight of the ethoxylated monoester was then copolymerised with Patented Aug. 15, 1961 i and more particularly 0.005 to 0.1% by weight of fuel type previously described and the. specific consumption of such an engine were investigated as a function of the smoke index when the engine was supplied with a fuel oil with, or without the addition of additive compositions according to the present invention.

7 The gas oil used had the following characteristics.

Density at F Engler Viscosity at C Sulphur, percent Cetane number The additive composition comprised 60% by weight of an ashless detergent and lead naphthenate and was added to the gas oil in quantities such that 1 kmg. of the gas oil contained 0.001 gm. atoms of lead.

The results of the experiment are summarised in Table II. a i e From the results it can be seen that for a given smoke index, for example, 6, the addition of the additive composition of the present invention to the gas oil results in:

' (1) A gain in output of from 6% to 12%.

(2) A decrease in specific consumption of from 2 Table I Titanium Thorium Lead Tin naphsulsul- Engine output Datum oleate-lthenate+ phonate phouate regulated to fuel oil dispersdispers- 7 (without (without ant A ant A dispersdispers ant A) ant A) Results deduced fromthis table;

Decrease of Gainin power specific conat 3.5 smoke sumption at index 3.5 smoke index Titanium 6% p 2.3 Tin+D1spersant 13, 13 6. 7 Thorium 6. 5, 6% 2. 1 Lead-i-Dispersant I 3, 13 3. 7

Table II Engine Supplied With- Gas oil-Head naphthenate+ Smoke Index Gas-oil Oopoly- Dispers- Monosul- Sulpho- Sulpho mat of ant A phate of mate of nate of meth- (Examethylene ethylene triethaacrylate pic I) diamine diamine nolamine alcohol 6 andamino alcohol 1. Engine Power in ELIE.

. II. Specific Consumption of Engine in grnmmesfH.P./hour.

What is claimed is:

1. A fuel oil containing from 0.001 to 0.5% by weight of a mixture of an oil soluble salt of a metal of group IV and from 10 to 75% by weight of an oil soluble ashless copolymer produced by copolymerizing 8 parts. of an ethoxylated monoester of C Oxo maleate with 37 parts of C Oxo m'aleofurnarate, 35 parts of O -C Oxo maleofumarate and 20 partsof vinyl acetate...

. 2.. A fuel oil composition as defined in claim 1 wherein said fuel oil is a petroleum distillate boiling above 400 F.

3. -A fuel oil composition as defined in claim 1 wherein said group IV metal is-lead.

. 4. A fuel oil composition as defined in said group IV metal is tin.

5. A fuel oil composition as definedin claim 1 wherein said oil soluble s'althas more than 6 carbon atoms per molecule. a

, 6. A fuel oil containing from 0.005 to 0.1% by weight of a mixture of from 40,60% by weight of tin naphthenate and from 40-60% by weight ofan oil soluble ashless copolymer produced by copolymen'zing 8 parts ofan ethoxylated monoester of C Oxo maleate with 37 parts of C Oxo maleofumarate, 35 parts of C -Cfl Oxo maleofumarate and 20 parts of vinyl acetate.

7. A fuel oil containing from 0.005 to 0.1% by weight ofa mixture of from -4060% by weight of lead oleate and from 4060% by weight of an oil soluble ashless copolymer produced by. copolymerizing 8v parts of an ethoxylated monoester of .C, Oxo maleate with 37 parts of C Oxo maleofumarate, 35 parts of (Z -C Oxo maleofumarate and 20 partsof vinyl acetate. a

. References Cited in the file of this patent.

claim wherein M 'UNITED STATES PATENTS 2,141,848 Adams et a1 Dec. 27, 1938 2,151,432 Lyons et al. Mar. .21, 1939 2,296,069 Talbert et a1, Sept. 15, 1942 2,338,578 Downing et al. Jan. 4, 1944 2,403,267 Davis ,Iuly 2, 1946 2,443,378 Dittrnar et al. June 15, 1948 2,524,864. Wies et al. a Oct. 10, 1950 2,560,542 Bartleson et al. July 17, 1951 2,575,003 Caron etal. Nov. 13, 1 951 2,684,292 Caron et al. July 20, 1954 a FOREIGN PATENTS 561,328" a Great Britain May 15, 1944 776,189 Great Britain June 5, 1957 

1. A FUEL OIL CONTAINING FROM 0.001 TO 0.5% BY WEIGHT OF A MIXTURE OF AN OIL SOLUBLE SALT OF A METAL OF GROUP IV AND FROM 10 TO 75% BY WEIGHT OF AN OIL SOLUBLE ASHLESS COPOLYMER PRODUCED BY COPOLYMERIZING 8 PARTS OF AN ETHOXYLATED MONOESTER OF C9 OXO MALEATE WITH 37 PARTS OF C9 OXO MALEOFUMARATE, 35 PARTS OF C16-C17 OXO MALEOFUMARATE AND 20 PARTS OF VINYL ACETATE. 